Tetrakisazo dyestuffs and processes for their production



nited States TETRAKISAZO DYESTUFFS AND PROCESSES FOR THEIR PRODUCTION No Drawing. Application May 7, 1956, Serial No. 582,929

Claims priority, application Switzerland May 17, 1955 8 Claims. (Cl. 260-166) The invention concerns tetraki'sazo dyestuffs which are suitable for the fast to light dyeing of cellulose fibres in yellow, orange to brown shades. The dyeings can be discharged well. It also concerns processes for the production of these new tetrakisazo dyestuffs as well as their use for the attainment of fast yellow, orange to brown cellulose dyeings and also, as industrial product, the material fast dyed with the aid of these dyestuffs.

It has been found that very valuable polyazo dyestufis are obtained by condensing two identical or different molecules of aminodisazo dyestuff of the general "Formula I tetrakisazo dyestuif of the general formula II:

In these formulae:

R1 represents a radical of the benzene or naphthalene series,

R2 represents a radical of the benzene or naphthalene series in which the azo linkages are in the p-position to each other,

R3 represents a radical of the benzene series in which the amino or acylamino group and the azo group are in the p-posit-ion to each other, and

Ar represents a p-phenylene radical.

In Formula I, at least one of the symbols R2 and Rs represents the radical of a 3-acylamino1-aminobenzene coupling component and the radicals R1 and R2 contain together at least two and at most three acid salt forming, water solubilising groups, for example sulphonic acid or carboxyl groups.

Amino disazo dyestuffs of the Formula I which are usable according to the present invention are obtained for example from diazotised aminobenzene and aminonaphthalene sulphonic and carboxylic acids by coupling with an azo component of the benzene or naphthalene series coupling in the p-position to a primary amino group. The diazotised aminobenzene and aminonaphthalene sulphonic and carboxylic acids mentioned above may contain one or two acid salt forming groups, and possibly a hydroxyl group in the o-position to a carboxyl group. Further admissible substituents are for example halogen, alkyl, alkoxy, acylamino, alkyl or aryl sulphonyl or sulphonic acid amide groups. In the above mentioned coupling, the use of a coupling component of the benzene series and in particular a l-amino-3-acylaminobenzene compound in this step is advantageous for the properties of the end product. Instead of the aminoazo dyestuffs obtained in this manner, also p-aminobenzene sulphonic acids can be used. These are obtained for example by sulphonating the basic compound or by coug as sodium acetate, di-

2,813,855 Patented Nov. 19, 1957 pling diazotised 4-nitro-1-amino or 4-acylamino-1-amino benzene or naphthalene sulphonic acids with 2-hydroxybenzene-l-carboxylic acids after converting the nitro or acylamino group into the primany amino group.

These p-aminoazo dyestulfs are further diazotised and coupled with azo components of the benzene series which couple in the p-position to a primary amino group, which advantageously do not contain any acid salt forming groups, e. g. l-aminobenzene, 2- or 3-methyl-, 2.5-dimethyl-, Z-methoxy-S-methyl-l-aminobenzene, or with a S-acyIamino-l-arrdnobenzene. If unsulphonated derivatives of the benzene and naphthalene series are used as first and second middle components corresponding to R2 and R3, the starting component must contain at least two acid water solubilising groups preferably two' sulphonic acid groups. In this case, aminobenzene and aminonaphthalene disulphonic acids are to be preferred as starting components. Also, possibly acid water solubilising groups canbe in the acyl radical of the 3-acylamino-1- aminobenzene component present according to the definition. This acyl radical can be derived from aliphatic dicarboxylic acids such as for example oxalic acid or succinic acid or from sulphonated fatty acids. Usually the radicals of low fatty acids or carbonic acid monoalkylester radicals form the acyl radical of this component.

Advantageously the condensation of the aminodisazo dyestutis with the benzene-p-dicarboxylic acid halides is performed with the aqueous solution of their alkali salts "at 10-60 in the presence or with the gradual addition of agents which butter or neutralise the mineral acid such or tri-sodium phosphate, sodium carbonate, caustic soda lye and magnesium oxide. Energetic stirring of the dyestutf solution is recommended. Possibly the presence of an organic solvent and acid binding agent to accelerate the condensation may be necessary, for example, pyridine or similar water soluble tertiary nitrogen bases. The benzene-p-dicarboxylic acid halides used may possibly also contain further inert substituents, for example halogen, alkyl or alkoxy groups.

The tetrakisazo dyestuffs according to the present invention can be isolated in a pure form, possibly after removal of the organic solvent with steam. They are easily obtained in the form of the alkali salts by carefully :salting out, any unchanged or unreacted acylated starting dyestuff being retained in solution.

In the form of their alkali salts, for example the lithium, sodium, potassium or ammonium salts, the new tetrakisazo dyestuffs are yellow to brown powders which dissolve well in water. According to the composition they draw well or very well onto cellulose fibres from an aqueous solution under the usual dyeing conditions in the presence of Glaubers salt. The yellow, orange to brown cellulose dyeings obtained therewith are distinguished by their very good fastness to light and they can be discharged well.

The following examples illustrate the invention without limiting it in any way. Where not otherwise stated, parts are given as parts by weight and the temperatures in degrees centigrade. The relationship of parts by weight to parts by volume is as that of kilograms to litres.

EXAMPLE 1 116.4 parts of the amino disazo dyestulf obtained by coupling diazotised 2-aminonaphthalene-6.8-disulphonic 1.4-dicarboxylic acid dichloride in 200 parts of acetone and an aqueous solution of sodium carbonate are added dropwise in such a manner that the reaction mixture always has a neutral reaction. As soon as no more free amine can be traced, the tetrakisazo dyestufi formed is precipitated by the addition of sodium chloride, filtered 01f, washed with diluted sodium chloride solution and dried. It is a brown powder which dissolves in water with a yellow-orange colour. It dyes natural or regenerated cellulose fibres in yellow-brown shades. The dyeings have very good fastness to light and can be discharged white.

The free acid of the new dyestufi corresponds to the formula:

' coin NE-CO-CH; HI SOaH NH-CO-CH:

It dissolves in concentrated sulphuric acid with a'blue colour which after some time changes to brown-red.

If in the above example, the components for the formation of the aminoazo dyestnfi are changed according to the following table, then dyestufls are obtained which have 30 filtered ofl, washed with diluted sodium chloride solution EXAMPLE 2 112.4 parts of the aminodisazo dyestuff of the formula:

50:13 NH-CO-O OH:

are dissolved with a neutral reaction in 1500 parts of water 10 with the addition of sodium hydroxide. 22.4 parts of benzene-lA-dicarboxylic acid dichloride dissolved in 200 parts of acetone are slowly added dropwise at 40-45 The hydrochloric acid which is split off during the reaction is continuously neutralised by the simultaneous addition dropwise of caustic soda lye. As soon as no more aminodisazo dyestufl can be traced, the tetrakisazo dyestulf formed is precipitated by the addition of sodium chloride,

similar properties. and dried.

Table Dyestufl 1st middle 2nd middle shade on colour colour of Nc.v Starting component component component acylating agent cotton 9. 11%?118 powder so u on 1 2-aminonophtha- 1-amino-3- i-amino-abenzene-1.4- yelloworange brown.

lone-6.8-disulmethylbenzene. carbomethoxydieerboxylic orange. phonic acid. arninobenzene. acid dichloride. 2 l-aminonaphthado 1-arnino-3- do do Do.

lenc-3.6-diacetylaminosnlphonic acid. benzene. 3 do 1-amin0-2- 1-amino-benzene d orange do red.

' methyI-5-acetyl amino-benzene. 4 1-aminonaphtha- 1-amino-3- l-amino-B- do red brown.

lane-3.8-disulacetylaminoacetlyamlno- U phonic acid. benzene. benzene. 5 Z-ammonaphtha- 1-arnino-3- 1-amino-3- 2.5-dimethyldo red-orange.-. D0.

lone-4.8-disulcarbomethoxy methylbenbenzene-1.4- phonic acid. aminobenzene. zene. dicarboxylic acid dichloride. 6. do 1-amino-3- 1-arnino-benzene benzene-1+ yelloworange redi butyroyldicarboxyitc orange.

aminobenzene. acid dichlore. 7 do l-amino-Z- l-arnino-3- do ornngeorangered-brown.

' methoxyl-5- formylred. red.

methylbenzene. aminobenzcne. 8 2-ammonaphtha- 1-amino-2.5- l-amino-3 2 5-dimethozy' red brown-red... brown.

Iene-SJ-disuldimethylhenzene. oarbomethbenzene-1.4- phonic acid. oxyaminodicarborylic benzene. acid dichloride. 9 do 1-amino-3- do benzene-1.4-diorange-red..- .do D0.

- carbomethoxycarboxylic acid aminobenzene. dichloride. 10 do 1-amino-8-sul- 1-amino-3- 2.5-dlchlorohenorange r red-brown.

phoacetylmethoxybenzene-1.4-dicaramiuobenzene. zene. boxylic acid dichloride. 1 1 z-eminonaphtha- 1-amin0-3-0xl-amino-2- benzene-iA-di- .-do do violet-brown.

' iene-3.6-disu1- alylaminobenmethoxy-5- cerboxylic acid phonic acid. zene. methylbenzene. dichloride. 12 o l-amino-2- 1-arnino-3- --do red-orange.-- do.... brown.

methoxy-5acmethyletylaminobenbenzene.

zone. is 2-aminonaphthal-arnino-3- l-arnino-B-cardo orange orange D0.

lene-5.7-disu1- methylbenzene. bethoxyaminophonic acid. benzene. i4 Z-aminonaphthado do do r red-brown.

lene.6-disull phonic acid. 15 2-aminonaphthal-amtno-Z-methl-amino-(ido do do Do.

' lenc-6.8-disuioxy-B-methylcarbornethphonic acid. benzene. oxyamlnobenzene.

In the free form, the new dyestufi corresponds to the formula:

It is a brown-red powder which dissolves in water with an orange red colour. The colour of the solution in concentrated sulphuric acid is blue at first but quickly changes to brown-olive. Dyed onto cotton or regenerated cellulose fibres, pure orange shades are obtained. The dyeings are very fast to light and can be discharged white.

If the 112.4 parts of aminodisazo dyestufi in the above example are replaced by the corresponding number of parts of one of the aminodisazo dyestuifs given in the following table, then dyestuffs are obtained which have similar properties.

aqueous solution of sodium carbonate are so added dropwise simultaneously at 10-15 that the reaction mixture CHI NH-C o-o-oH. I n.

always has a neutral reaction. On completion of'the dropwise addition, the whole is stirred. until no more amino disazo dyestufi' can: be traced. The new tetraki'sazo dyestufi obtained of the. formula:

SOaH

Dye- Shade Colour Colour Stufi Aminodisazo dyestufl Acylating agent on aqueous of N0. cotton solution powder 1 E0 8 N= N=N NHr benzeue-lA-dicarorange red orange. red brown.

boxylic acid (11- chloride. SOaH NH-C O-GHa 2 H0=N=NQN=N NH: do do -d0 brow-n.

SOaH NH-C O-O-CaHt-O-CH:

3 nmsOn: QN=N NH'T do do red.. red brown.

SO H NHC OO-C'-2Hu SIOaH 4 HO-QN= QN=NQNH1 do do red orange.- brown.

OOH Ha NHO OOCH; SOaH (3H1 5 H0 N= N=N NH: do red orange recL Do.

1 COOH 0-CH; NH-C O-OCHi CH: CH:

..... SOaH I IHC o-o-cirn-o-on,

EXAMPLE 3 106.4 parts of the aminodisazo dyestutf l-aminobenzene- 2.5-disulphonic acid- 1-amino-3-acetylaminobenzene 1- amino-3-methylbenzene are dissolved; with a neutral. reaction in 1500 parts of water with the addition of sodium carbonate. A solution of. 22.4 parts ofibenzene-lA-dicarboxylic acid dichloride in 200 parts of acetone and an position 1-aminobenzene-2.S-disulphonic acid 1amino- 3-acetylaminobenzenel-amino-3 -methylbenzene,. one of the combinations given in the following table is condensed with-a benzene-lA-dicarboxylic acid'diehloride according to the above example, then dyestuffs are obtained which 75 have similar properties.

Table Dyestufi 1st middle 2nd middle shade on oolour colour of No. Starting component component component aoylating agent cotton aqluetous powder sou on 1 l-amlnobenzenel-amlno-B-methyl- 1-amino-3-acetylbenzene-lA-dlcaryellow-orange. orange red.

2.5-disulphonio benzene. amlnobenzene. boxylic acid diacid. chloride. 2 .do l-amino-Ii-tormyl- ---do do orange red red-brown.

amlnobenzene. 3 d 1-amino-3-carbo- Lnmmobenzene --do yellow-orangered.

methoxyaminobenzene. 4 -do l-amlno-Z-methoxyl-amlno-e-methyldo orange red red-brown.

o-acetylaminobenzene. benzene. 5 l-aminobenzenel-aminonaphtha- 1-amlno-3-ecetyldo red-brown..." brown-redbrow-n.

, i-sulphonic acid. leriigJ-sulphonle aminobenzene.

ac 6 l-aminobenzenel-amino-a sulphm 1-amlno-3-methyldo yellow-orange. orange red.

3-sulphonie acid. goetyl-amlnobenzene.

enzene. 7 --do l-aminoa-oxalyl- 1-am1nobenzeno 2.5-dimethylbenorange red brown.

aminobenzene. zene-M-dicarboxyllc acid dichloride. 8 1-am1no-2.4-dido l-amino-Z-rnetboxy- 2.5-dlchlorobenzenered-orange." do brown-violet.

methylbenzene- B-methylbenzene. iA-dicarboxylic fi-sulphonio acid. acid dichloride. 9 l-amlnobenzenedo l-amlno-S-methylbenzene-1.4-dicerreddish orange red-brown.

3-carboxylie acid. benzene. bgiryliig acid dlyellow.

0 or e. 10 1-nmino-4-nitro- 1-nmlno-3-sulphol-amlnobenzene do red-orange. red brown-violet.

benzene-il-caraoetylaminoboxylic acid. benzene. r 11 l-aminobenzene- 1-nmino-3-acetyll-amino-a-methyldo reddish orange red-orange.

2-eerboxylie acldaminobenzene. benzene. yellow. d-sulphonic acid. 12 do l-amlno-Z-meth- 1-am1nobenzene -.-do orange red brown. oxy-E-acetylaminobenzene. I3 l-amlnobenzene- 1-amino-3-methyll-amino-3-carbodo yellow orangeorange red.

Beulphonic acid. benzene. methoxyethylaminobenzene. 14 l-arninobenzene- 1-amlno-3-acetyll-nmino-z-metboxydo red-orange red red-brown.

2,5ikdisulphonio nminobenzene. b-methylbenzene. ec 15 l-arnlnobenzene- 1-amin0napbthalene- 1-amlno-3-ecetylblnelshred do brown.

4-sulphonie acid. fi-sulphonie acid. amlnobenzene. 16 l-arninobenzene- -do 1-amino-3-carbored -.d0 D0.

3-sulphon1c acid. {)nethoxyaminoenzene. 17 l-aminobenzenel-aminonapbthaleneh 1-emino-3-aeetyl-- do yellowishrei. do red-brown.

zjfiiisulphonle aminobenzene. ac 18 do do 1-amin0-3-carbo- -..do do .-do Do.

ethoxy-aminobenzene. 19 -do 1-nmlno-3-tormyl- 1-amino-3-acetyl- 2.5-dimethoxyorange -do D0.

aminobenzene. aminobenzene. benzene-1.441-

carboxylic acid dichloride.

EXAMPLE 4 1s precipitated by the addltion of sodium chloride, filtered I s- 582 parts of the anunodlsazo dyesmfl of the formula: and washed with d1luted sodium chloride solution It d1 solves in water with an orange colour and In concentrated S0111 Wm QM-Q NH-GO-CH:

and 53.2 parts of the aminodisazo dyestutf of the formula:

SOsH

sulphuric acid with a greenish-blue colour. It dyes natuml or regenerated cellulose fibres in pure yellow-orange shades which are very fast to light and can be discharged white.

Further similar dyestuiis are obtained if in the above example, the 58.2 parts of the aminodisazo dyestufi of the formula:

are replaced by the equivalent number of parts of one of the dyestufis given in the table at the end of Example 1.

EXAMPLE 5 SOaH 9 r a 1'0 30 minutes, 45 parts of sodium sulphate are added and wherein: dyeing is continued for 60 minutes at this temperature. The goods are then rinsed in cold water and dried in the usual way. The cotton is dyed in yellow-orange shades which have very good. fastness to light.

What we claim is:

1'. A tetrakisazo dyestufi? having the general formula:

R1 represents an aromatic radical containing at least one six-membered carbocyclic nucleus and at most two such nuclei condensed with one another,

R2 represents a mononuclear radical of the benzene series, containing the azo groups in p-position to eachother and containing X1 in o-position to the azo group con- 1 i Heating R1 anclRz,

B E S E E Ra represents a mononuclear radical of the benzene series 3 2 containing the groups N=N- and NH- bound wherein thereto in p-position to each other and X2 in o-position R and R' each re rese t an aromati 'r di a1 t the' N=Nl group menflqned least sixjjemgered carbocyzlig i i z jg ii Ar represents a mononuclear radlcal of the benzene series most two such nuclei condensed with one another, g a 7 g m the 0 R2 and Rz each represent an aromatic radical containing 0 1 an d at eas one represen s an my mm at least one six-membered carbocyclic nucleus and at group an most two such nuclei condensed with one another c0nwhereby the radicals R1 and R2 together contain at least taining the azo groups in p-position to each other, two and at most three acid water solubilising groups.

R3 and R's each represent a mononuclear radical of the 3. A tetrakisazo dyestutf having the general formula:

Y: V V Y2 Y1 l I Y: H0;si-N=N -N=N-QNH-o o }c ONHQN=N- %-N=NASO3H X1 Z X9 X: Z 1

benzene series in which the bonds shown stand in the wherein:

p-position to each other, Ar represents a mononuclear radical of the benzene series A if; 2 :33: g i g g fi g f g gg the group conslst contalmng the CO groups m 08mm of X1 and X2, one X represents an acylamino group and h b of R2 and R3 and and at least one the other X represents a member selected from the symbol in each group represents a 1,4-phenylene-2-acy1- group conslstmg of hydrogen, the acylammo and amino radical and each of the radicals R1 and R2 and 35 methyl g p R'1 and R'z together contain at least two and at most of Y1 and 2, 0116 Y represents the a group and the three acid water solubilising groups. other Y represents hydrogen, and

2. A tetrakisazo dyestufi having the general formula: Z and V each represent a member selected from the R -N=N-1'1,-N=N-1|h-NHC 0-Ar-O ONH-R3N=NR2N=NR1 40 group consisting of hydrogen, the methyl and the meth- Xl X, l I oxy group.

4. A tetrakisazo dyestufi having the formula soda 1113 an, S0311 N=N-QN= QNH-C 0G0 o-NHO-N=NON= 6 son: NH-CO-CH; 0H ()CH, 11THO0CH3 803B 5. A tetrakisazo dyestufi having the formula soil: 803E M MQNMO MHQW M SOaH NH-C O-CH: Ha a NH-CO-OHa SOBH 6. A tetrakisazo dyestuif having the formula 7. A tetrakisazo dyestufi having the formula I 0 H3 (EH3 S 03H SOaH OCH: NH-C O-O-CHs I OCH: SOaH 2,818,855- "11 12 8. A tetrakisazo dyestufi having the formula Y 7 z 7' 1 $9 3 Y w j Referenes Cited in the file of this patent UNITED STATES PATENTS 7 1,913,333 Gubelmann et al. June 13, 1933 2,746,954 Grandjean et al May 22, 1956 1 I sod! Ha NH-co-cm v r NH-co-cm In sofl 

1. A TETRAKISAZO DYESTUFF HAVING THE GENERAL FORMULA: 